# Patent

## Title
Structural metal-clad polymer article

## Abstract

Metal-clad polymer articles containing structural fine-grained and/or amorphous metallic coatings/layers optionally containing solid particulates dispersed therein. The fine-grained and/or amorphous metallic coatings are particularly suited for strong and lightweight articles, precision molds, sporting goods, automotive parts and components exposed to thermal cycling although the CLTE of the metallic layer and the one of the substrate is mismatched. The interface between the metallic layer and the polymer is suitably pretreated to withstand thermal cycling without failure.

## Background
FIELD OF THE INVENTION
This invention relates to metal-clad polymer articles comprising polymeric materials having a coefficient of linear thermal expansion exceeding 25×10−6 K−1 in at least one direction and fine-grained (average grain-size: 2-5,000 nm) or amorphous metallic materials having a coefficient of thermal expansion below 25×10−6 K−1 enabled by the enhancement of the pull-off strength between the metallic material and the polymer. The metal-clad polymer articles with mismatched coefficients of thermal expansion display good adhesion between the metallic layers and the polymeric materials as well as excellent thermal cycling performance and are suitable for structural applications.
BACKGROUND OF THE INVENTION
The invention relates to metal-clad polymer articles comprising amorphous or fine-grained metallic coatings/layers on polymeric composite materials/substrates with good adhesion and thermal cycling performance for use in structural applications.
Due to their low cost and ease of processing/shaping by various means, polymeric materials, which are optionally filled with, or reinforced with, materials selected from the group of metals, metal alloys, and/or carbon based materials selected from the group of graphite, graphite fibers, carbon, carbon fibers and carbon nanotubes, glass, glass fibers and other inorganic fillers, are widely used.
Applying metallic coatings or layers to the surfaces of polymer parts or vice versa is of considerable commercial importance because of the desirable properties obtained by combining polymers and metals. Metallic materials, layers and/or coatings are strong, hard, tough and aesthetic and can be applied to polymer substrates by various low temperature commercial process methods including electroless deposition techniques and/or electrodeposition. The metal deposits must adhere well to the underlying polymer substrate even in corrosive environments and when subjected to thermal cycling and loads, as encountered in outdoor or industrial service.
The prior art describes numerous processes for metalizing polymers to render them suitable for metal deposition by conditioning the substrate's surface to ensure metal deposits adequately bond thereto resulting in durable and adherent metal coatings. The most popular substrate conditioning/activation process is chemical etching.
Stevenson in U.S. Pat. No. 4,552,626 (1985) describes a process for metal plating to fill thermoplastic resins such as Nylon-6®. The filled resin surface to be plated is cleaned and rendered hydrophilic and preferably deglazed by a suitable solvent or acid. At least a portion of the filler in the surface is removed, preferably by a suitable acid. Thereafter electroless plating is applied to provide an electrically conductive metal deposit followed by applying at least one metallic layer by electroplating to provide a desired wear resistant and/or decorative metallic surface. Stevensen provides no information on thermal cycling performance or adhesion strength.
Leech in U.S. Pat. No. 4,054,693 (1977) discloses processes for the activation of resinous materials with a composition comprising water, permanganate ion and manganate ion at a pH in the range of 11 to 13 exhibiting superior peel strengths following electroless metal deposition. Leech provides no information on thermal cycling performance, and adhesion strength is exclusively measured using a peel test.
Yates in U.S. Pat. No. 5,863,410 (1999) describes an electrolytic process for producing copper foil having a matte surface with micropeaks with a height not greater than about 200 microinches ( ̃5 micron) exhibiting a high peel strength when bonded to a polymeric substrate.
Various patents address the fabrication of articles for a variety of applications:
Erb in U.S. Pat. No. 5,352,266 (1994), and U.S. Pat. No. 5,433,797 (1995), assigned to the same applicant, describe a process for producing nanocrystalline materials, particularly nanocrystalline nickel. The nanocrystalline material is electrodeposited onto the cathode in an aqueous acidic electrolytic cell by application of a pulsed current.
Palumbo in U.S. Patent Publication No. 2005/0205425 A1 (2002) and DE 10,288,323 (2005), assigned to the same applicant, discloses a process for forming coatings or freestanding deposits of nanocrystalline metals, metal alloys or metal matrix composites. The process employs tank plating, drum plating or selective plating processes using aqueous electrolytes and optionally a non-stationary anode or cathode. Nanocrystalline metal matrix composites are disclosed as well.
Tomantschger in U.S. Ser. No. 12/003,224 (2007), assigned to the same applicant, discloses variable property deposits of fine-grained and amorphous metallic materials, optionally containing solid particulates.
Palumbo in U.S. Pat. No. 7,320,832 (2008), assigned to the same applicant, discloses means for matching the coefficient of thermal expansion (CTE) of fine-grained metallic coating to the one of the substrate by adjusting the composition of the alloy and/or by varying the chemistry and volume fraction of particulates embedded in the coating. The fine-grained metallic coatings are particularly suited for strong and lightweight articles, precision molds, sporting goods, automotive parts and components exposed to thermal cycling and include polymeric substrates. Maintaining low CTEs (<25×10−6 K−1) and matching the CTEs of the fine-grained metallic coating with the CTEs of the substrate minimizes dimensional changes during thermal cycling and preventing delamination. Palumbo provides no information on the adhesion strength.
Palumbo in U.S. Pat. No. 7,354,354 (2008), assigned to the same applicant, discloses lightweight articles comprising a polymeric material at least partially coated with a fine-grained metallic material. The fine-grained metallic material has an average grain size of 2 nm to 5,000 nm, a thickness between 25 micron and 5 cm, and a hardness between 200 VHN and 3,000 VHN. The lightweight articles are strong and ductile and exhibit high coefficients of restitution and a high stiffness and are particularly suitable for a variety of applications including aerospace and automotive parts, sporting goods, and the like. Palumbo provides no information on thermal cycling performance or adhesion strength.
SUMMARY OF THE INVENTION
It is an objective of the present invention to provide strong, lightweight metal-clad polymer articles for use in structural applications, e.g., in automotive, aerospace and defense applications, industrial components, electronic equipment or appliances and sporting goods, molding applications and medical applications having a metallic layer applied to a polymeric substrate with enhanced adhesion, pull-off strength, peel strength, shear strength and thermal cycling performance.
It is an objective of the invention to provide a metallic coating/layer selected from the group of amorphous, fine-grained and coarse-grained metal, metal alloy or metal matrix composites. The metallic coating/layer is applied to the polymer substrate by a suitable metal deposition process. Preferred metal deposition processes include low temperature processes, i.e., processes operating below the softening and/or melting temperature of the polymer substrates, selected from the group of electroless deposition, electrodeposition, physical vapor deposition (PVD), chemical vapor deposition (CVD) and gas condensation. Alternatively, the polymer can be applied to a metallic layer. The metallic material represents between 5 and 95% of the total weight of the article.
It is an objective of the present invention to provide single or multiple structural metallic layers having a microstructure selected from the group of fine-grained, amorphous, graded and layered structures, which have a total thickness in the range of between 10 micron and 5 cm, preferably between 25 micron and 2.5 cm and more preferably between 50 micron and 500 micron.
It is an objective of the invention to provide a metal-clad polymer article comprising a shaped or molded polymer component comprising polymeric resins or polymeric composites including, but not limited to, epoxies, ABS, polypropylene, polyethylene, polystyrene, vinyls, acrylics, polyamide and polycarbonates. Suitable fillers include carbon, ceramics, oxides, carbides, nitrides, polyethylene, fiberglass and glass in suitable forms including fibers and powders. The polymeric substrate has a room temperature coefficient of linear thermal expansion (CLTE) in at least one direction of between 30×10−6 K−1 and 500×10−6 K−1, e.g., of between 30×10−6 K−1 and 250×10−6 K−1.
It is an objective of this invention to provide a fine-grained and/or amorphous metallic layer having a room temperature CLTE in all directions of less than 25×10−6 K−1, for example, in the range between −5.0×10−6 K−1 and 25×10−6K−1. The metallic layer comprises one or more elements selected from the group of Ag, Al, Au, Co, Cr, Cu, Fe, Ni, Mo, Pb, Pd, Pt, Rh, Ru, Sn, Ti, W, Zn and Zr. Metal matrix composites consist of fine-grained and/or amorphous pure metals or alloys with suitable particulate additives. The latter additives include powders, fibers, nanotubes, flakes, metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V, and Zn; nitrides of Al, B and Si; C (graphite, diamond, nanotubes, Buckminster Fullerenes); carbides of B, Cr, Bi, Si, W; and self lubricating materials such as MoS2 or organic materials e.g. PTFE. The fine-grained and/or amorphous metallic material has a high yield strength (300 MPa to 2,750 MPa) and ductility (1-15%).
It is an objective of the invention to utilize the enhanced mechanical strength and wear properties of fine-grained metallic coatings/layers with an average grain size between 1 and 5,000 nm, e.g., between 2 and 500 nm, and/or amorphous coatings/layers and/or metal matrix composite coatings exhibiting a coefficient of linear thermal expansion (CLTE) in the range of −5×10−6 K−1 to 25×10−6K−1 at room temperature in all directions. Metal matrix composites (MMCs) in this context are defined as particulate matter embedded in a fine-grained and/or amorphous metal matrix. MMCs can be produced e.g. in the case of using an electroless plating or electroplating process by suspending particles in a suitable plating bath and incorporating particulate matter into the deposit by inclusion or, e.g., in the case of cold spraying, by adding non-deformable particulates to the powder feed.
It is another objective of the invention to provide laminate articles, e.g., a metal-clad polymer article, comprising (i) a polymeric material which at room temperature has a coefficient of linear thermal expansion in the range between 30×10−6K−1 and 250×10−6 K−1 in at least one direction and (ii) a metallic material having a microstructure which is fine-grained with an average grain size between 2 and 5,000 nm and/or an amorphous microstructure, the metallic material being in the form of a metallic layer having a thickness between 10 microns and 2.5 cm and a coefficient of linear thermal expansion in all directions in the range between −5.0×10−6 K−1 and 25×10−6 K−1, the coefficient of linear thermal expansion in all directions of (ii) being at least 20% less than the coefficient of linear thermal expansion in at least one direction of (i), the laminate article and metal-clad polymer article exhibiting no delamination and the displacement of said metallic material relative to the polymeric material or relative to any intermediate layer being less than 2% after said articles has been exposed to at least one temperature cycle according to ASTM B553-71 service condition 1, 2, 3 or 4 and exhibiting a pull-off strength between the polymeric material and the metallic material or between any intermediate layer(s) and the metallic material exceeding 200 psi as determined by ASTM D4541-02 method A-E.
It is another objective of the invention to pretreat the surface of polymeric and/or the metallic material to achieve excellent adhesion between metallic layer and the polymer material.
It is an objective of the invention to suitably roughen or texture at least one of the surfaces to be mated to form specific surface morphologies, termed “anchoring structures” or “anchoring sites”. The elimination of smooth surfaces provides for additional surface area for adhesion, increases the bond strength and reduces the risk of delamination and/or blistering.
It is an objective of the invention to provide a polymer metal interface by creating suitable anchoring structures prior to applying the metal to the polymer or vice versa. The population of anchoring sites such as recesses/protrusions and the like enhances the physical bond between the polymer and the metal. It is an objective to create anchoring structures at the interface between the polymer and the metal exceeding 10 per cm, preferably exceeding 100 per cm and more preferably exceeding 1,000 per cm and up to 100,000 per cm, preferably up to 1,000,000 per cm and more preferably up to 10,000,000 per cm. Suitable anchoring structures have an average depth and average diameter/width in the range of between 0.01 and 5,000 micron. The overall strength of the metal-clad polymer article is governed by the bond strength between the polymer substrate and the immediately adjacent metallic layer.
It is another objective of the invention to provide laminate articles for components exposed to temperature cycling during use thereby increasing the need for acceptable CLTE mismatch between polymer and the metallic materials.
It is an objective of the invention to provide a polymeric or metallic substrate with an interface layer having a surface roughness Ra in the range of between 0.01 μm and 500 μm and/or Ry (Rymax according to DIN) in the range of 0.01 μm and 5,000 μm. In the context of this application the average surface roughness Ra is defined as the arithmetic means of the absolute values of the profile deviations from the mean line and Ry (Rymax according to DIN) is defined as the distance between the highest peak and the lowest valley of the interface surface.
It is an objective of the invention to apply a fine-grained and/or amorphous metallic coating to at least a portion of the surface of a part made substantially of polymer(s) and/or glass fiber composites and/or carbon/graphite fiber composites including carbon fiber/epoxy composites, optionally after metallizing the surface (layer thickness ≦5 micron, preferably ≦1 micron) with a thin layer of nickel, copper, silver or the like for the purpose of enhancing the electrical conductivity of the substrate surface. The fine-grained and/or amorphous coating is always substantially thicker (≧10 micron) than the metallizing layer. Any metalizing intermediate layer has a coefficient of linear thermal expansion (CLTE) in the range of −5.0×10−6 K−1 to 25×10−6 K−1 at room temperature in all directions.
According to this invention patches or sleeves which are not necessarily uniform in thickness can be employed in order to, e.g., enable a metallic thicker coating on selected sections or areas of articles particularly prone to heavy use such as in the case of selected aerospace and automotive components, sporting goods, consumer products, electronic devices and the like.
It is an objective of the invention to achieve adhesion strength as measured using ASTM D4541-02 Method A-E “Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers” between the metallic material/coating and the polymer material/substrate which exceeds 200 psi, preferably 300 psi, preferably 500 psi and more preferably 600 psi and up to 6,000 psi.
It is an objective of the invention to suitably precondition the polymer substrate surface to enhance the adhesion between the polymer substrate and the metallic layer and achieve a strong interfacial bond between the polymer and the metal.
It is an objective of the invention to improve the adhesion between the polymeric substrate and the metallic layer by a suitable heat treatment of the metal-clad article for between 5 minutes and 50 hours at between 50 and 200° C.
It is an objective of this invention to provide articles composed of fine-grained and/or amorphous metallic coatings on composite polymeric substrates capable of withstanding 1, preferably 5, more preferably 10, more preferably 20 and even more preferably 30 temperature cycles without failure according to ANSI/ASTM specification B604-75 section 5.4 (Standard Recommended Practice for Thermal Cycling Test for Evaluation of Electroplated Plastics ASTM B553-71) for service condition 1, preferably service condition 2, preferably service condition 3 and even more preferably for service condition 4.
It is an objective of this invention to provide lightweight polymer/metal-hybrid articles with increased strength, stiffness, durability, wear resistance, thermal conductivity and thermal cycling capability.
It is an objective of this invention to provide polymer articles, coated with fine-grained and/or amorphous metallic layers that are stiff, lightweight, resistant to abrasion, resistant to permanent deformation, do not splinter when cracked or broken and are able to withstand thermal cycling without degradation, for a variety of applications including, but not limited to: (i) applications requiring cylindrical objects including gun barrels; shafts, tubes, pipes and rods; golf and arrow shafts; skiing and hiking poles; various drive shafts; fishing poles; baseball bats, bicycle frames, ammunition casings, wires and cables and other cylindrical or tubular structures for use in commercial goods; (ii) medical equipment including orthopedic prosthesis and surgical tools crutches, wheel chairs and medical equipment including orthopedic prosthesis, implants and surgical tools; (iii) sporting goods including golf shafts, heads and faceplates; lacrosse sticks; hockey sticks; skis and snowboards as well as their components including bindings; racquets for tennis, squash, badminton; bicycle parts; (iv) components and housings for electronic equipment including laptops; TVs and handheld devices including cell phones; personal digital assistants (PDAs) devices; walkmen; discmen; MP3 players and BlackBerry®-type devices; cameras and other image recording devices as well as TVs; (v) automotive components including heat shields; cabin components including seat parts, steering wheel and armature parts; fluid conduits including air ducts, fuel rails, turbocharger components, oil, transmission and brake parts, fluid tanks and housings including oil and transmission pans; cylinder head covers; spoilers; grill-guards and running boards; brake, transmission, clutch, steering and suspension parts; brackets and pedals; muffler components; wheels; brackets; vehicle frames; spoilers; fluid pumps such as fuel, coolant, oil and transmission pumps and their components; housing and tank components such as oil, transmission or other fluid pans including gas tanks; electrical and engine covers; (vi) industrial/consumer products and parts including linings on hydraulic actuator, cylinders and the like; drills; files; knives; saws; blades; sharpening devices and other cutting, polishing and grinding tools; housings; frames; hinges; sputtering targets; antennas as well as electromagnetic interference (EMI) shields; (vii) molds and molding tools and equipment; (viii) aerospace parts and components including wings; wing parts including flaps and access covers; structural spars and ribs; propellers; rotors; rotor blades; rudders; covers; housings; fuselage parts; nose cones; landing gear; lightweight cabin parts; cryogenic storage tanks; ducts and interior panels; wings, rotors, propellers and their components and (ix) military products including ammunition, armor as well as firearm components, and the like; that are coated with fine-grained and/or amorphous metallic layers that are stiff, lightweight, resistant to abrasion, resistant to permanent deformation, do not splinter when cracked or broken and are able to withstand thermal cycling without degradation.
It is an objective of this invention to at least partially coat the inner or outer surface of parts including complex shapes with fine-grained and/or amorphous metallic materials that are strong, lightweight, have high stiffness (e.g. resistance to deflection and higher natural frequencies of vibration) and are able to withstand thermal cycling without degradation.
Accordingly, the invention in one embodiment denoted the first embodiment, is directed to a metal-clad polymer article comprising:

    
    
        (i) a polymeric material which at room temperature has a coefficient of linear thermal expansion in the range between 30×10−6 K−1 and 250×10−6 K−1 in at least one direction; and
        (ii) a metallic material having a microstructure which is fine-grained with an average grain size between 2 and 5,000 μm and/or an amorphous microstructure, the metallic material being in the form of a metallic layer having a thickness between 10 micron and 2.5 cm and a coefficient of linear thermal expansion in all directions in the range between −5.0×10−6 K−1 and 25×10−6 K−1;
        (iii) with or without at least one intermediate layer between the polymeric material and the metallic material (having a coefficient of linear thermal expansion in all directions in the range between −5.0×10−6 K−1 and 250×10−6 K−1;
        (iv) an interface between the polymeric material and the metallic material or an interface between the polymeric material and any intermediate layer(s) and an interface between any intermediate layer(s) and the metallic material;
        (v) anchoring structure at said interface(s) comprising recesses and/or protrusions to increase the interface area and provide enhanced physical bond at the interface between the polymeric material and the metallic material or at the interface between the polymeric material and any intermediate layer;
        (vi) said metal-clad polymer article exhibiting no delamination and the displacement of said metallic material of (ii) relative to the polymeric material of (i) or relative to any intermediate layer(s) being less than 2% after said article has been exposed to at least one temperature cycle according to ASTM B553-71 service condition 1, 2, 3 or 4; and
        (vii) said metal-clad polymer article exhibiting a pull-off strength between the polymeric material of (i) and the metallic material of (ii) or any intermediate layer exceeding 200 psi as determined by ASTM D4541-02 Method A-E; and
        (viii) said metal-clad polymer article or portion thereof having a yield strength and/or ultimate tensile strength of between 10 and 7,500 MPa and an elastic limit between 0.5 and 30%.
    
    


Accordingly, the invention in another embodiment, denoted second embodiment, is directed to a metal-clad polymer article comprising:

    
    
        (i) a polymeric material which at room temperature has a coefficient of linear thermal expansion in the range between 30×10−6 K−1 and 250×10−6 K−1, in at least one direction;
        (ii) a metallic material having a microstructure which is fine-grained with an average grain size between 2 and 5,000 nm and/or an amorphous microstructure, the metallic material being in the form of a metallic layer having a thickness between 10 micron and 2.5 cm and a coefficient of linear thermal expansion in all directions in the range between −5.0×10−6 K−1 and 25×10−6 K−1, the coefficient of linear thermal expansion in all directions being at least 20% less than the coefficient of linear thermal expansion in at least one direction of (i);
        (iii) with or without at least one intermediate layer between the polymeric material and the metallic material having a coefficient of linear thermal expansion in all directions in the range between −5.0×10−6 K−1 and 250×10−6 K−1, the coefficient of linear thermal expansion in all directions of (ii) being at least 20% less than the coefficient of linear thermal expansion in at least one direction of (i);
        (iv) an interface between the polymeric material and the metallic material or an interface between the polymeric material and any intermediate layer(s) and an interface between any intermediate layer(s) and the metallic material;
        (v) anchoring structure at said interface(s) comprising recesses and/or protrusions to increase the interface area and provide enhanced physical bond at the interface between the polymeric material and the metallic material or at the interface between the polymeric material and any intermediate layer;
        (vi) said metal-clad polymer article exhibiting no delamination and the displacement of said metallic material of (ii) relative to the polymeric material of (i) being less than 2% after said article has been exposed to at least one temperature cycle according to ASTM B553-71 service condition 1, 2, 3 or 4; and
        (vii) said metal-clad polymer article exhibiting a pull-off strength between the polymeric material of (i) and the metallic material of (ii) or any intermediate layer exceeding 200 psi as determined by ASTM D4541-02 Method A-E; and
        (viii) said metal-clad polymer article or portion thereof having a yield strength and/or ultimate tensile strength of between 10 and 7,500 MPa and an elastic limit between 0.5 and 30%.
    
    


Accordingly the invention in still another embodiment it denoted the third embodiment is directed to a method for preparing the metal-clad polymer article of the first embodiment comprising:

    
    
        (i) providing a polymeric material which at room temperature has a coefficient of linear thermal expansion exceeding 30×10−6 K−1 in at least one direction.
        (ii) providing a metallic material having a microstructure which is fine-grained with an average grain size between 2 and 5,000 nm and/or an amorphous microstructure where the metallic material is in the form of a metallic layer having a thickness between 10 microns and 2.5 cm and a coefficient of linear thermal expansion in all directions in the range between −5.0×10−6 K−1 and 25×10−6 K−1,
        (iii) optionally providing at least one electrically conductive or electrically nonconductive adhesive intermediate layer,
        (iv) providing interface(s) between the polymeric material and the metallic layer and between the polymeric material and any intermediate layer and between any intermediate layer and the metallic layer and between any adjacent intermediate layers,
        (v) providing anchoring structure at said interfaces to anchor polymeric material to metallic layer or polymeric material to any intermediate layer, and metallic layer to any intermediate layer or in the case of intermediate layers to anchor one intermediate layer to another.
    
    


In one aspect of the third embodiment the coefficient of linear thermal expansion in all directions of the metallic layer and of any intermediate layer(s) is at least 20% less than the coefficient of linear thermal expansion in at least one direction of the polymeric material. In one case of the third embodiment a metallic layer is deposited onto a polymeric substrate having anchoring structure associated therewith by electrodeposition, physical vapor deposition (PVD), and chemical vapor deposition (CVD). In another case of the third embodiment the polymeric material is applied to the metallic layer having anchoring structure associated therewith.
As used herein, the terms “laminate article” and “metal-clad article” means an item which contains at least one polymeric layer and at least one metallic layer in contact with each other.
As used herein, the term “coating” means deposit layer applied to part or all an exposed surface of a substrate.
As used herein, the term “coating thickness” or “layer thickness” refers to depth in a deposit direction.
As used herein, “anodically assisted chemical etching” means that the surface of a polymeric substrate to be coated is activated by applying anodic polarization to the substrate which is submersed in a chemical etching solution thereby simultaneously chemically and electrochemically activating the surface to achieve a superior bond between the substrate and the subsequently applied coating.
As used herein, the term “anchoring structures” refers to surface features including recesses/protrusions purposely created in the interface between the polymeric material and the metallic material layer or the interface between the polymeric material and the intermediate layer, e.g., in the polymeric material or in the metallic material layer or in any intermediate layer, to enhance their bond strength.
As used herein, the term “population of anchoring structures” refers to number of surface features per unit length or area. The “linear population of anchoring structures” can be obtained by counting the number of features, e.g. on a cross sectional image and normalizing it per unit length, e.g., per cm. The average “areal population of anchoring structures” is the square of the average linear population, e.g., expressed in cm2 or mm2. Alternatively, the average areal density can be obtained by counting the number of features visible in an optical micrograph, SEM image or the like and normalizing the count for the measurement area.
As used herein, “surface roughness”, “surface texture” and “surface topography” mean an irregular surface topography such as a polymer material or metallic material layer or intermediate layer surface containing anchoring structures. Surface roughness consists of surface irregularities which result from the various surface preconditioning methods used such as mechanical abrasion and etching to create suitable anchoring structures. These surface irregularities/anchoring structures combine to form the “surface texture” which directly influences the bond strength achieved between the polymeric article and the metallic layer.
In practice there are many different parameters used for analyzing surface finish, and many more have been developed for special products/circumstances. The parameter most frequently used in North America for surface roughness is Ra. It measures the average roughness by comparing all the peaks and valleys to the mean line, and then averaging them all over the entire length that a stylus is dragged across the surface. It's also referred to as CLA (center line average) and AA (area average). Benefits of using the Ra method are its simplicity and its widespread use. The RMS (root mean square) of a given surface typically runs about 10% higher than its equivalent Ra (average roughness) value.
In reality, however, the Ra value neither provides a detailed enough description of a surface finish of a part nor an absolute indication of the achievable adhesion strength when bonded to another material. Another parameter that can be useful is Rymax formerly called just Rmax. This is an ISO standard that measures the distance between the highest peak and the lowest valley over a cutoff length. This is, however, a sensitive method and, if over the measurement length a scratch or imperfection is encountered, the reading may be meaningless. Similarly, Ry depicts the maximum roughness depth.
Another parameter most widely used in Europe is Rz, or mean roughness depth. The Rz ISO standard is also called “Ten Point Average Roughness”. It averages the height of the five highest peaks and the depth of the five lowest valleys over the measuring length, using an unfiltered profile. The Rz DIN standard averages the highest point and lowest point over five cutoffs.
As used herein, the term “intermediate layer” means a layer located between and in intimate contact with a polymeric material substrate and a metallic layer or another intermediate layer. Examples of intermediate layers include “intermediate conductive layers” or “metalizing layers” applied to the surface of the polymer material to enhance the surface to enable electroplating. The intermediate layer can comprise a metallic layer, an oxide layer, a polymeric material layer such as an adhesive layer, or a polymer layer with conductive particulates embedded therein.
As used herein, the term “molding” of polymers means shaping of an article to its near final shape using injection molding, blow molding, compression molding, transfer molding, rotational molding, extrusion, thermoforming, vacuum forming or other suitable shaping methods available for polymers.
As used herein “delamination” means failure of a laminated structure by the separation between two layers comprised of different chemical compositions resulting in the physical splitting of the layers.
As used herein “displacement” means the difference between a later position of a coating and its original position on a substrate caused by the relative movement of a coating, e.g., induced by thermal cycling of laminates composed of layers with different CLTEs.
According to one aspect of the present invention an article is provided by a process which comprises the steps of, positioning the metallic or metallized work piece to be plated in a plating tank containing a suitable electrolyte and a fluid circulation system, providing electrical connections to the work piece/cathode to be plated and to one or several anodes and plating a structural layer of a metallic material with an average grain size of equal to or less than 5,000 μm on the surface of the metallic or metallized work piece using suitable direct current (D.C.) or pulse electrodeposition processes described, e.g., in the copending application US Patent Publication No. US2005-020542A1, published Sep. 22, 2005 (DE 10,288,323; 2005).
Metal-clad polymer articles of the invention comprise fine-grained and/or amorphous metallic layers having low CLTEs e.g. −5.0×10−6K−1 to 25×10−6 K−1 in all directions, having a layer thickness of at least 0.010 mm, preferably more than 0.020 mm, more preferably more than 0.030 mm and even more preferably more that 0.050 mm on polymeric substrates having CLTEs in at least one direction of between 30×10−6 K−1 to 500×10−6 K−1.
Articles of the invention comprise a single or several fine-grained and/or amorphous metallic layers applied to the substrate as well as multi-layer laminates composed of alternating layers of fine-grained and/or amorphous metallic layers and polymeric substrates.
The fine-grained metallic coatings/layers have a grain size under 5 μm (5,000 nm), preferably in the range of 5 to 1,000 nm, more preferably between 10 and 500 nm. The grain size can be uniform throughout the deposit; alternatively, it can consist of layers with different microstructure/grain size. Amorphous microstructures and mixed amorphous/fine-grained microstructures are within the scope of the invention as well.
According to this invention, the entire polymer surface can be coated; alternatively, metal patches or sections can be formed on selected areas only (e.g. golf club face plates or sections of golf club shafts, arrows or polymer cartridge casings), without the need to coat the entire article.
According to this invention metal patches or sleeves which are not necessarily uniform in thickness and/or microstructure can be deposited in order to e.g. enable a thicker coating on selected sections or sections particularly prone to heavy use such as golf club face or sole plates, the tip end of fishing poles, arrows and shafts for golf clubs, skiing or hiking poles, polymer cartridge casings, automotive components and the like.
According to this invention laminate articles in one aspect comprise fine-grained and/or amorphous metal layers on carbon-fiber and/or glass fiber filled polymeric substrates.
The following listing further defines the laminate article/metal-clad article of the invention:
Polymeric Substrate Specification:


    Minimum coefficient of linear thermal expansion in at least one dimension [10−6 K−1]: 25; 30; 50
    Maximum coefficient of linear thermal expansion in at least one dimension [10−6 K−1]: 250; 500
    Polymeric materials comprise at least one of: unfilled or filled epoxy, phenolic or melamine resins, polyester resins, urea resins; thermoplastic polymers such as thermoplastic polyolefins (TPOs) including polyethylene (PE) and polypropylene (PP); polyamides, mineral filled polyamide resin composites; polyphthalamides, polyphthalates, polystyrene, polysulfone, polyimides; neoprenes; polybutadienes; polyisoprenes; butadiene-styrene copolymers; poly-ether-ether-ketone (PEEK); polycarbonates; polyesters; liquid crystal polymers such as partially crystalline aromatic polyesters based on p-hydroxybenzoic acid and related monomers; polycarbonates; acrylonitrile-butadiene-styrene (ABS); chlorinated polymers such polyvinyl chloride (PVC); and fluorinated polymers such as polytetrafluoroethylene (PTFE). Polymers can be crystalline, semi-crystalline or amorphous.
    Filler additions: metals (Ag, Al, In, Mg, Si, Sn, Pt, Ti, V, W, Zn); metal oxides (Ag2O, Al2O3, SiO2, SnO2, TiO2, ZnO); carbides of B, Cr, Bi, Si, W; carbon (carbon, carbon fibers, carbon nanotubes, diamond, graphite, graphite fibers); glass; glass fibers; fiberglass metallized fibers such as metal coated glass fibers; mineral/ceramic fillers such as talc, calcium silicate, silica, calcium carbonate, alumina, titanium dioxide, ferrite, mica and mixed silicates (e.g. bentonite or pumice).
    Minimum particulate/fiber fraction [% by volume]: 0; 1; 5; 10
    Maximum particulate/fiber fraction [% by volume]: 50; 75; 95

Metallic Coating/Metallic Layer Specification:

    Minimum coefficient of linear thermal expansion [10−6 K−1]: −5.0; −1.0; 0
    Maximum coefficient of linear thermal expansion [10−6 K−1]: 15; 20; 25
    Microstructure: Amorphous or crystalline
    Minimum average grain size [nm]: 2; 5; 10
    Maximum average grain size [nm]: 100; 500; 1,000; 5,000; 10,000
    Metallic layer Thickness Minimum [μm]: 10; 25; 30; 50; 100
    Metallic layer Thickness Maximum [mm]: 5; 25; 50
    Metallic materials comprising at least one of: Ag, Al, Au, Co, Cr, Cu, Fe, Ni, Mo, Pb, Pd, Pt, Rh, Ru, Sn, Ti, W, Zn and Zr
    Other alloying additions: B, C, H, O, P and S
    Particulate additions: metals (Ag, Al, In, Mg, Si, Sn, Pt, Ti, V, W, Zn); metal oxides (Ag2O, Al2O3, SiO2, SnO2, TiO2, ZnO); carbides of B, Cr, Bi, Si, W; carbon (carbon nanotubes, diamond, graphite, graphite fibers); glass; polymer materials (PTFE, PVC, PE, PP, ABS, epoxy resins)
    Minimum particulate fraction [% by volume]: 0; 1; 5; 10
    Maximum particulate fraction [% by volume]: 50; 75; 95
    Minimum Yield Strength Range [MPa]: 300
    Maximum Yield Strength Range [MPa]: 2,750
    Minimum Hardness [VHN]: 100; 200; 400
    Maximum Hardness [VHN]: 800; 1,000; 2,000
    Minimum Deposition Rates [mm/hr]: 0.01; 0.05; 0.1; 0.2; 0.5

Intermediate Layer Specification:

    Metallic Layer: composition selected from metallic materials list set forth above, including electroless Ni, Cu, Co and/or Ag comprising coatings; metallic layers can contain an oxide layer on the outer surface, which can promote the bond strength to the polymer substrate.
    Oxide layer: oxides of elements as listed in the metallic materials list, including Ni, Cu, Ag oxides
    Polymeric Layer: composition selected from polymeric materials list including partly cured layers prior to coating and finishing heat treatment, also cured polymeric paint (carbon, graphite, Cu, Ag filled curable polymers, adhesive layer.
    Intermediate Layer Thickness Minimum [μm]: 0.005; 0.025;
    Intermediate Layer Thickness Maximum [μm]: 1; 5; 25; 50

Interface Specification (Polymer/Intermediate Layer Interface or Polymer/Metallic Layer Interface):

    Minimum surface roughness Ra, Ry, Rymax, Rz [μm]: 0.01; 0.02; 0.05; 0.1; 1
    Maximum surface roughness Ra, Ry, Rymax, Rz [μm]: 25; 50; 500; 5,000
    Minimum linear population of anchoring surface structures [number per cm]: 10; 100; 1,000
    Maximum linear population of anchoring surface structures [number per cm]: 105; 106; 107 
    Minimum areal population of anchoring surface structures [number per mm2]: 1, 100; 104 
    Maximum areal population of anchoring surface structures [number per mm2]: 107; 1010 
    Minimum anchoring structure diameter [nm]: 10, 50, 100
    Maximum anchoring structure diameter [μm]: 500; 1,000
    Minimum anchoring structure height/depth [nm]: 10, 50, 100
    Maximum anchoring structure height/depth [μm]: 500; 1,000
    Anchoring surface structure topography: recesses; protrusions; “inkbottle type” cavities; pitted anchoring surface structures; holes; pores; depressions; anchoring surfaces with protruding anchoring fibers; grooved, roughened and etched anchoring surface structures; nodules; dimples; mounds; as well as honeycomb or open foam type structures; “brain”, “cauliflower”, “worm”, “coral” and other three dimensionally interconnected porous surface structures. Typically any number of different anchoring structures is present in the suitably textured surface, their shapes and areal densities can be irregular and the clear identification of individual anchoring structures can be subject to interpretation. The most reliable method therefore to account for the effect of anchoring structures is to measure the adhesion property of the metal-clad polymer article, e.g., using the ASTM D4541-02 pull-off strength test.

Metal-clad Polymer Article Specification:

Adhesion:

    Minimum pull-off strength of the coating according to ASTM D4541-02 Method A-E [psi]: 200; 300; 400; 600
    Maximum pull-off strength of the coating according to ASTM D4541-02 Method A-E [psi]: 2,500; 3,000; 6,000

Thermal Cycling Performance:

    Minimum thermal cycling performance according to ASTM B553-71: 1 cycle according to service condition 1 without failure (no blistering, delamination or <2% displacement) and with <2% displacement between the polymer and metallic material layers.
    Maximum thermal cycling performance according to ASTM B553-71: infinite number of cycles according to service condition 4 without failure.

Metal-clad Polymer Article Mechanical Properties:

    Polymer substrate weight fraction of the metal-clad polymer article [%]: 5 to 95
    Minimum yield strength of the metal-clad polymer article [MPa]: 5; 10; 25; 100
    Maximum yield strength of the metal-clad polymer article [MPa]: 5,000; 7,500.
    Minimum ultimate tensile strength of the metal-clad polymer article [MPa]: 5; 25; 100
    Maximum ultimate tensile strength of the metal-clad polymer article [MPa]: 5,000; 7,500
    Minimum elastic limit of the metal-clad polymer article [%]: 0.5; 1
    Maximum elastic limit of the metal-clad polymer article [%]: 5; 10, 30


The following description summarizes the test protocols used:
Adhesion Test Specification:
ASTM D4541-02 “Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers” is a test for evaluating the pull-off strength of a coating on rigid substrates determining the greatest perpendicular force (in tension) that a coating/substrate interface surface area can bear before it detaches either by cohesive or adhesive failure. This test method maximizes tensile stress as compared to shear stress applied by other methods, such as scratch or knife adhesion and the results may not be comparable. ASTM D4541-02 specifies five instrument types identified as test Methods A-E and the pull off strength reported is an average of at least three individual measurements.
Thermal Cycling Test Specification:
ANSI/ASTM specification B604-75 section 5.4 Test (Standard Recommended Practice for Thermal Cycling Test for Evaluation of Electroplated Plastics ASTM B553-71). In this test the samples are subjected to a thermal cycle procedure as indicated in Table 1. In each cycle the sample is held at the high temperature for an hour, cooled to room temperature and held at room temperature for an hour and subsequently cooled to the low temperature limit and maintained there for an hour.







TABLE 1







Standard Recommended Practice for Thermal Cycling Test for


Evaluation of Electroplated Plastics According to ASTM B553-71











Service Condition
High Limit [° C.]
Low Limit [° C.]







1 (mild)
60
−30



2 (moderate)
75
−30



3 (severe)
85
−30



4 (very severe)
85
−40










If any blistering, delamination or cracking is noted the test is immediately suspended. After 10 such test cycles the sample is allowed to cool to room temperature, is carefully checked for delamination, blistering and cracking and the total displacement of the coating relative to the substrate is determined.


DETAILED DESCRIPTION
This invention relates to laminate articles comprising structural metallic material layers on polymeric substrates that are suitably shaped to form a precursor of the metal-clad polymer article. The metallic materials/coatings are fine-grained and/or amorphous and are produced by DC or pulse electrodeposition, electroless deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD) and gas condensation or the like. The intrinsic mismatch of the coefficient of thermal expansion of the metal and the polymer of the inventive metal-clad polymer articles is overcome and acceptable thermal cycling performance achieved by enhancing the pull-off strength between the metallic material and the polymer by suitable surface activation and/or surface roughness and/or metal-polymer interface surface design.
The person skilled in the art of plating will know how to electroplate or electroless plate selected fine-grained and/or amorphous metals, alloys or metal matrix composites choosing suitable plating bath formulations and plating conditions. Similarly, the person skilled in the art of PVD, CVD and gas condensation techniques will know how to prepare fine-grained and/or amorphous metal, alloy or metal matrix composite coatings.
Applying metallic coatings to polymer and polymer composite parts is in widespread use in consumer and sporting goods, automotive and aerospace applications. Polymer composites with carbon/graphite and/or glass fibers are relatively inexpensive, easy to fabricate and machine; however, they are not very durable. Metallic coatings are therefore frequently applied to polymers and polymer composites to achieve the required mechanical strength, wear and erosion resistance and to obtain the desired durability and service life. To achieve the required durability of laminate articles excellent bond strength between the metallic layer and the polymer substrate is of paramount importance.
A variety of fine-grained and/or amorphous metallic coatings, which at room temperature have a coefficient of thermal expansion in the range between minus 5.0×10−6 K−1 and 25×10−6 K−1 in all directions, can be employed. Particularly suited are fine-grained and/or amorphous high-strength pure metals or alloys containing Ag, Al, Au, Co, Cr, Cu, Fe, Ni, Mo, Pb, Pd, Pt, Rh, Ru, Sn, Ti, W, Zn and Zr; and optionally one or more elements selected from the group consisting of B, C, H, O, P and S; and/or optionally containing particulate additions such as metal powders, metal alloy powders and metal oxide powders of Ag, Al, Au, Cu, Co, Cr, Fe, Ni, Mo, Pd, Pt, Sn, Rh, Ru, Ti, W, Zn and Zr; nitrides of Al, B and Si; C (graphite, carbon fibers, carbon nanotubes or diamond); carbides of B, Cr, Bi, Si, W; ceramics, glasses and polymer materials such as polytetrafluoroethylene (PTFE), polyvinylchloride (PVC), acrylonitrile-butadiene-styrene (ABS), polyethylene (PE), polypropylene (PP). The particulate average particle size is typically between 500 nm and 5 μm.
Metallic coatings can have a coarse-grained, fine-grained or amorphous microstructure. One or more metallic coating layers of a single or several chemistries and microstructures can be employed. The metallic coating can be suitably exposed to a finishing treatment, which can include, among others, electroplating, i.e., chromium plating and applying a polymeric material, i.e., paint or adhesive.
Polymeric substrates, for the most part have a CLTE significantly exceeding 25×10−6 K−1 in at least one direction. Selected polymeric materials and particularly filled or reinforced polymeric materials, can display coefficient of thermal expansion values which are not isotropic, but vary significantly with the direction. As an example, glass filled polyamide can have coefficient of linear thermal expansion (CLTE) values as low 20-75×10−6 K−1 in one direction and as high as 100-250×10−6 K−1 in another direction. In the case of fiber reinforced polymer materials, as fibers usually align in the plane of the part during molding, the CLTE of the polymer in the plane is typically lower than the CLTE perpendicular/normal to it. The degree of CLTE match or CLTE mismatch between the coating and the substrate and the bond strength between the coating and the substrate play an important role in preventing delamination and affecting the relative coating/substrate displacement in industrial composite parts exposed to thermal cycling. To clarify, the stronger the bond strength between the polymer and the metallic material the more CLTE mismatch and the higher the temperature fluctuations the metal-clad polymer article can endure. It is therefore of crucial importance to suitably roughen/pretreat/activate the polymeric surface to ensure the bond strength to the coatings and particularly metallic coatings is optimized. Of course, mechanical properties of the substrate and coating are important as well, particularly the yield strength, ultimate tensile strength, resilience and elongation.
Suitable polymeric substrates include unfilled or filled epoxy, phenolic and melamine resins, polyester resins, urea resins; thermoplastic polymers such as thermoplastic polyolefins (TPOs) including polyethylene (PE) and polypropylene (PP); polyamides, mineral filled polyamide resin composites; polyphthalamides; polyphthalates, polystyrene, polysulfone, polyimides; neoprenes; polybutadienes; polyisoprenes; butadiene-styrene copolymers; poly-ether-ether-ketone (PEEK); polycarbonates; polyesters; liquid crystal polymers such as partially crystalline aromatic polyesters based on p-hydroxybenzoic acid and related monomers; polycarbonates; acrylonitrile-butadiene-styrene (ABS); chlorinated polymers such polyvinyl chloride (PVC); and fluorinated polymers such as polytetrafluoroethylene (PTFE).
These polymeric substrates are frequently reinforced by adding suitable fillers including carbon, carbon nanotubes, graphite, graphite fibers, carbon fibers, metals, metal alloys, glass and glass fibers; fiberglass, metallized fibers such as metal coated glass fibers and the like. Appropriate filler additions in the substrate range from as low as 2.5% per volume or weight to as high as 95% per volume or weight. In addition to fillers with a high aspect ratio, other fillers such as glass, ceramics and mineral fillers such as talc, calcium silicate, silica, calcium carbonate, alumina, titanium dioxide, ferrite, and mixed silicates (e.g. bentonite or pumice) can be employed as well.
Particularly suitable substrates include carbon/graphite fiber and glass fiber resin composites in which the resin components include phenolic resins, epoxy resins, polyester resins, urea resins, melamine resins, polyimide resins, polyamide resins as well as elastomers such as natural rubber, polybutadienes, polyisoprenes, butadiene-styrene copolymers, polyurethanes, and thermoplastics such as polyethylene, polypropylene, and the like.
During molding/shaping of the precursor metal-clad article, polymer chains do not necessarily align themselves in a random manner but rather display directionality depending on part geometry, molding conditions, material flow patterns etc. Similarly, fiber additions usually align in the plane and the electrical and thermal conductivities of such composites in a plane can be 10-100 times higher than perpendicular to the plane. Therefore, directional properties need to be considered in metal-clad polymer articles. Furthermore, non uniformity of the molded polymer or polymer matrix composite substrates can at times be exacerbated near the surface and significant differences in composition and properties near the outer surface layer, which participates in forming the bond to a coating layer and the interior bulk of the molded polymer, can exist.
To enhance the bond between the metallic layer, i.e., the metallizing/intermediate layer or the fine-grained/amorphous metallic layer and the polymer, polymeric surfaces forming the interface with the metallic layer are typically preconditioned before the metallic layers are applied. Numerous attempts have been made to identify, characterize and quantify desired surface features which result in achieving the desired bonding properties and to quantify the surface topography and surface roughness in quantifiable scientific terms. Heretofore, these efforts have not succeeded in part because of the complexity of the surface features, the numerous parameters such as population, size and shape of the anchoring structures which affect the mechanical interlocking. Furthermore, it is not even clear if the bond strength between metals and polymers is entirely dictated by mechanical forces or if chemical interactions, e.g., between functional surface groups of the polymers present or introduced during etching, contribute to the bond strengths as typically after etching the wetting angle is reduced due to the creation of hydrophilic functional groups, i.e., —COOH and —COH. Similarly, the metal surface at the interface can be at least partially oxidized which at times can enhance the adhesion.
Anchoring structures are surface features induced on the polymeric surface by the various surface preconditioning methods used including, but not limited to, mechanical abrasion, swelling, dissolution, chemical etching and plasma etching, and furthermore depend on the composition of the polymer substrate and the amount, size and shape of fillers employed. In practice when dealing with polymeric and metallic surfaces that are pretreated to improve adhesion, surface features are usually quite irregular and difficult to describe/measure in absolute terms and attempts to quantify surface features responsible for good adhesion between the coating and the substrate have not been successful to date. Alternatively, as outlined in another preferred embodiment the polymer can be applied to a suitably rough metal substrate.
Over time a variety of standardized tests measuring adhesion have been developed and results from one test are frequently not comparable with results obtained with another test. The most popular test for adhesion between the metallic coating and a polymer substrate are peel tests. The force measured to peel a thin coating off the substrate relates to a force required to propagate debonding and before the test is initiated the coating is purposely debonded from the substrate. Peel tests measure the interfacial fracture energy and are used to characterize adhesive and thin metal coatings (decorative coatings) up to a thickness of 20 microns. When the thickness and the strength of the coatings increase, e.g., in the case of thick structural coatings/layers employing fine-grained metallic coatings, peel tests do not provide meaningful results. Pull-off tests, on the other hand, measure the force required to debond a unit area of the interface of the substrate and the coating and, in the case of metal-clad polymer articles with structural metallic layers, they are more relevant as the objective is to increase the force required for initiation of debonding as much as possible. In contrast to peel tests, pull-off test results are unaffected by the coating thickness. As illustrated in selected examples below there is no reliable correlation between pull-off and peel strength data.
Ways are sought to enable tolerating a larger CLTE mismatch between a metallic coating/layer and polymeric materials/substrates employed in strong, lightweight and structural laminate/metal-clad polymer articles as the bond strength achieved remains significantly below the one achieved between metallic coatings and metallic substrates. As the appropriate surface preparation of the substrate is known to have a significant impact on the bond strength and adhesion, the preferred approach is to provide means of substantially enhancing the bond strength between the metallic layer and the polymer. As highlighted, the surface topography created during the pretreatment procedure has a significant effect on adhesion. Ideally, when employing surface pretreatment methods, anchoring structures selected from the group of “inkbottle type” cavities, pitted anchoring surface structures, nodules, anchoring surfaces with protruding anchoring fibers, grooved, roughened and etched anchoring surface structures are formed at the interface between the metallic layer and the polymeric substrates and interlock the metallic and polymer layers raising the adhesion strength. The number, population density, shape, size and depth of anchoring structures greatly affects the bond strength achievable and therefore standardized adhesion tests are required to determine and objectively compare bond quality such as ASTM D4541-02.
Platable polymeric compositions therefore frequently employ “removable fillers” which are extracted from the near surface of the metal-polymer interface by a suitable pretreatment prior to metal deposition. In the case of polymer composites containing “permanent fibers” pretreatment methods and conditions can be optimized to “expose” some of the embedded fibers to enable the coating to adhere thereto and, at least partially encapsulate them, again resulting in enhanced bond strength and in an increase in CLTE mismatch between the coating and the substrate that can be tolerated. Many suitable polymeric compositions therefore contain both removable and permanent fillers. Leaching of the removable fillers alone without the creation of additional anchoring structures has been determined not to create a sufficiently high population of anchoring structures to meet the pull-off strength requirement of the metal-clad polymer article.
Desired metallic material-polymeric material interface surface features can be generated in a shaped polymer precursor article or a metallic layer in several ways:
1. Mechanical Surface Roughening of the Polymer and/or Metal Interface:
The surface of the substrate to be coated can be suitably roughened by a mechanical process, e.g., by sanding, grid blasting, grinding and/or machining.
2. Imprinting of the Polymer Surface by Molding and/or Other Shaping Methods:
Desirable anchoring structures can be imprinted/patterned on the surface of the substrate to be coated by suitable polymer molding, stamping, forming and/or shaping methods applying pressure to the soft, softened or molten polymer surface, including but not limited to injection and compression molding, and “print rolling” which transfer the desired texture to the polymer substrate surface.
3. Chemical Etching of the Polymer and/or Metal Interface Near-Surface:
Chemical etching using oxidizing chemicals such as mineral acids, bases and/or oxidizing compounds such as permanganates is the most popular method for etching polymers practiced in industry. This method also benefits from the use of “platable polymer grades” which contain filler materials which, in the near outer surface layer, are dissolved during the etching process.
The co-pending application by McCrea entitled “Anodically Assisted Chemical Etching of Conductive Polymers and Polymer Composites” discloses a surface activation process for conductive polymers/polymer composites consisting of simultaneously applying anodic polarization and chemical etching, referred to as “anodically-assisted chemical-etching” or “anodic assisted etching”. This process drastically enhances the bond strength between the activated substrate and the applied coating. Simultaneous chemical and electrochemical etching of polymeric substrates substantially enhances the bond, peel and shear strength between the polymeric substrate and the applied metallic coating/layer as highlighted in the co-pending application.
Solvent free chemical etching can be employed as well, to etch and/or suitably texture the outer surface including plasma etching or etching with reactive gases including, but not limited to, SO3 and O3, to suitably precondition and texture the surface.
4. Swelling of the Polymeric Substrate Surface:
Application of swelling agents to create anchoring structures in the near surface of the polymer with or without the use of etching and abrasion methods can be employed. Suitable swelling agents include organic solvents for one or more polymers in the substrate.
5. Applying Adhesive Layers or Partially Cured Polymeric Substrates:
Where applicable, partly cured polymer substrates may be activated and coated, followed by an optional curing heat treatment. Similarly, adhesive layers may be applied between the polymeric substrate and the metallic coating which can also be followed by an optional curing heat.
6. Post Cure Treatment of Metal-Clad Polymer Articles:
Another process that can be used to to improve the adhesion between the polymeric substrate and the metallic layer entails a suitable heat treatment of the metal-clad article for between 5 minutes and 50 hours at between 50 and 200° C.
7. Applying the Polymer to a Rough Metal Surface:
Another approach entails first forming the metallic layer with one surface to be covered by the polymer purposely “roughened” and containing suitable surface features/protrusions/surface roughness to create anchoring structures elevating from the metallic surface, recessing into the metal surface or their combinations, to aid in enhancing the adhesion to the polymeric substrate. In this case the polymeric material is applied onto the metallic material and not vice-versa.
Combinations of two or more of the aforementioned processes can be used as well and the specific pretreatment conditions typically need to be optimized for each polymer and molded part to maximize the bond strength which can be conveniently determined using the pull off test described.
As highlighted, carbon-fiber and/or graphite-fiber and/or glass-fiber (referred to as carbon/graphite/glass-fiber) polymer composite molds are popular for sporting goods, automotive and aerospace parts and for fabricating composite prototypes for the aerospace industry. Carbon/graphite/glass-fiber polymer composite molds are cheap but lack durability and therefore find use only for prototyping. Depositing, e.g., fine-grained and/or amorphous metals such as Ni, Co, Cu and/or Fe-based alloys onto the carbon/graphite-fiber polymer composite molds provides for tremendous cost savings over the traditional approach of machining and forming Invar molds.
Similarly, carbon/graphite-fiber polymer composites are also a popular choice for aerospace components including plane fuselage, wings, rotors, propellers and their components as well as other external structures that are prone to erosion by the elements including wind, rain, hail and snow or can be damaged with impact by debris, stones, birds and the like. Aerospace and defense applications particularly benefit from a strong, tough, hard, erosion-resistant fine-grained and/or amorphous coating. Lightweight laminate articles are also employed in internal airplane parts.
Suitable laminate metallic-material/polymeric-material articles include, but are not limited to, precision graphite fiber/epoxy molds used in aerospace, automotive and other industrial applications that are exposed to repeated temperature cycling (between −75° C. and up to 350° C.). Metal-clad polymer parts made from the fine-grained and/or amorphous metallic coatings on appropriate substrates are well suited for high precision molding components requiring great dimensional stability over a wide operating temperature range.
In applications where coatings are applied to substrates it is usually desired for the coefficient of linear thermal expansion (CLTE) of, e.g., the metal coating to be closely matched to the CLTE of the polymeric substrate or polymer composite to avoid delamination/failure during thermal cycling. Similarly in molding applications (blow, injection, compression molding and the like) good matching of the thermal expansion properties of all components is conventionally required to avoid spring-back and delamination during the heating and the cooling cycle. The tolerable “CLTE mismatch” between the metallic layer and the polymer depends on the application, the quality of the adhesion between the coating and the polymer substrate, the maximum and minimum operating temperature and the number of temperature cycles the article is required to withstand in its operating life. In all instances, after a predetermined number of thermal cycles, consisting either of submersing the article in liquid nitrogen for one minute followed by submersion in hot water for one minute, or other suitable thermal cycling tests including ANSI/ASTM specification B604-75 section 5.4 Test (Standard Recommended Practice for Thermal Cycling Test for Evaluation of Electroplated Plastics ASTM B553-71), the coating relative to the underlying substrate should not fail. Delamination, blistering or cracking of the coating and/or the substrate which would compromise the appearance or performance of the article are all considered failure. Similarly, a displacement of the coating relative to the underlying substrate of more than 2% constitutes failure.
Suitable permanent substrates include polymeric materials filled with or reinforced with e.g. graphite or glass which reduces the CLTE in at least the plane of the polymeric substrate. For added strength, durability and high temperature performance filled polymers are very desirable. The term “filled” as used herein refers to polymer resins which contain fillers embedded in the polymer, e.g., fibers made of graphite, carbon nanotubes, glass and metals; powdered mineral fillers (i.e., average particle size 0.2-20 microns) such as talc, calcium silicate, silica, calcium carbonate, alumina, titanium oxide, ferrite, and mixed silicates. A large variety of filled polymers having a filler content of up to about 95% by weight are commercially available from a variety of sources. If required, e.g., in the case of electrically non-conductive or poorly conductive substrates and the use of electroplating for the coating deposition, the substrates can be metallized to render them sufficiently conductive for plating.
As highlighted, a number of processes can be used to form the metal-clad polymer articles. In the case of using electroplating to apply the metallic layer to the polymer substrate, the polymer substrate, after suitably being appropriately shaped and activated, is preferably metallized to enhance the surface conductivity typically by applying a thin layer called the “intermediate conductive layer” or “metalizing layer”. The intermediate conductive layer can comprise a metallic layer or can comprise polymeric material with conductive particulates therein. Where the intermediate conductive layer comprises a metallic layer, the metallic layer is constituted of Ag, Ni or Cu or a combination of any two or all of these, and the intermediate conductive layer can be deposited by electroless deposition, sputtering, thermal spraying, chemical vapor deposition, physical vapor deposition of by any two or more of these. Where the intermediate conductive layer comprises polymeric material with conductive particulates therein, it can be, for example, a conductive paint or a conductive epoxy. The conductive particulates can be composed of or contain Ag, Ni or Cu or graphite or other conductive carbon or a combination of two or more of these. As highlighted the surface of the metal layer or metal particulates can be oxidized to enhance adhesion.
The following working examples illustrate the benefits of the invention, specifically a comparison of pull-off and peel strength data for two sets of metal-clad polymer samples processed the same way, namely ABS polymeric substrate coated with an organic adhesive layer that is partially cured, then coated with a Ag intermediate layer and a fine-grained Ni—Fe layer, followed by heat treatment to fully cure the part (Working Example I); mechanically abraded graphite-fiber epoxy substrates coated with fine-grained nickel (Working Example II); chemically and anodically etched carbon fiber cloth reinforced bismaleimide substrates, then coated with a Ag intermediate layer and coated with a fine-grained nickel-iron alloy (Working Example III); chemically etched graphite-fiber and glass fiber reinforced polymer substrates coated with nickel-based materials with an amorphous or fine-grained microstructure using an intermediate conductive Ag layer (Working Example IV); coating of fully-cured and partially-cured graphite reinforced polymer composites with a silver (Ag) intermediate layer and a fine-grained Ni layer, including heat treatment of the partially-cured coated part (Working Example V); coating of a chemically etched glass fiber reinforced polyamide polymer composite with a Ni—P intermediate layer with a fine-grained Ni metal, followed by a post-plating heat-treatment (Working Example VI); and a polypropylene backing layer applied to a fine-grained Co—P metal layer with a rough interface surface produced electrochemically (Working Example VII). Intermediate metallizing layers were used in Working Examples I, III, IV, V and VI.
The invention is illustrated by the following working examples.
WORKING EXAMPLE I
(Comparison of pull-off and peel strength for high density ABS substrate coated with an adhesive layer, then metallized with an Ag intermediate layer and a fine-grained Ni—Fe layer with and without heat treatment of the coated part)
Two 10×15 cm coupons were cut from a commercial 6 mm ABS sheet (CLTE:  ̃75×10−6 K−1 in all directions) The coupons were ground on one side with 80 grit SiC paper to a consistent surface roughness. The samples were then cleaned with Alconox and steel wool, followed by ultrasonically cleaning in deionized water for 5 minutes. The samples were rinsed in isopropanol, dried and degreased with 1,2-dichloroethane to remove any residual oils and/or films.
Subsequently, the coupons were coated on one side with a thin film of a commercial epoxy-based adhesive available from Henkel Canada, Brampton, Ontario (LePage 11). The epoxy based adhesive coating was then partially cured at room temperature for 2 hours. Thereafter the panels were chemically etched at 65° C. for 5 minutes in alkaline permanganate solution (M-Permanganate P, Product Code No. 79223) available from MacDermid Inc. of Waterbury, Conn., USA. Following etching, the samples were rinsed in deionized water and submerged in neutralizer solution (M-Neutralize, Product Code No. 79225 also available from MacDermid Inc.) for 5 minutes at room temperature. After neutralizing, the samples were rinsed with deionized water and metalized using a commercial silvering solution (available from Peacock Laboratories Inc., of Philadelphia, Pa., USA; average grain size 28 nm) and coated with 20 μm of fine-grained Ni-58Fe (average grain size  ̃20 nm, CLTE:  ̃2×10−6 K−1) according to the process of U.S. Patent Publication No. U.S. 2005-0205425 A1, published Sep. 22, 2005, the whole of which is incorporated herein by reference.
The metal clad articles had a yield strength of 44.6 MPa, an ultimate tensile strength of 47.3 MPa, a Young's modulus of 2.4 GPa and an elastic limit of 1.8%.
One of the panels was then subjected to a post-coating curing treatment consisting of heat treating the sample in a drying oven for an additional 2 hours at 50° C. to fully cure the adhesive film. Pull-off and peel adhesion strength of the coatings on the two samples was then measured following ASTM D4541-02 “Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers” using the “PosiTest AT Adhesion Tester” available from the DeFelsko Corporation of Ogdensburg, N.Y., USA and ASTM B533-85 (2004) “Standard Test Method for Peel Strength of Metal Electroplated Plastics” using an Instron 3365 testing machine equipped with the 90 degree peel test fixture, and a 5KN load cell, available from Instron Corporation, Norwood, Mass., USA. In all cases debonding occurred between the polymer material surface and the immediately adjacent metal layer.
The pull-off and peel adhesion strength for the two samples is summarized in the table below. While the pull-off strength was high and essentially the same for both samples, the sample that received a post-coating heat treatment to fully cure the adhesive film displayed a much higher peel strength (more than three fold). This example illustrates that pull off tests and peel tests are not interchangeable and do not produce results which are comparable. Specifically to this example, as highlighted, pull-off strength exceeding 1,000 psi is considered “excellent” for structural metal-clad polymer parts. A peel strength value of 4 N/cm (Newton/cm), in the case of decorative metal coatings on polymers, is considered to be “very poor”, whereas a peel strength value of 12.5 N/cm is considered “excellent”.







TABLE 2







Pull-Off Strength Data (ASTM D4541-02) and Peel Strength


Data (ASTM B533-85) for Samples With and Without Post


Cure Heat Treatment.










Pull-off Strength (ASTM
Peel Strength (ASTM



D4541-02) [psi]
B533-85) [N/cm]













Sample 1 without post-
1075
4.0


cure heat treatment


Sample 2 with post-
1100
12.5


cure heat treatment









Similar results were obtained when the intermediate layer comprised “electroless Ni”, available from various commercial vendors and consisting of amorphous Ni—P, with a P content ranging from 2-15%, including Ni-7P available from MacDermid Inc., Waterbury, Conn., USA.
WORKING EXAMPLE II
Fine-grained Ni Coated Graphite Reinforced Composite Activated by Mechanical Abrasion
6 mm thick graphite fiber/epoxy sheets were sourced from Newport Adhesives and Composites, Irvine, Calif., USA, and were cut into 5 cm by 5 cm coupons. The surface of the coupons was mechanically ground using P1000 sandpaper exposing carbon fibers. The CLTE of the coupon in the plane was 5×10−6K−1 and normal to the plane 60×10−6 K−1. After surface preparation the surface roughness of the coupons was determined to be Ra  ̃2.0 micron and Rymax ̃10.0 micron. Microscope analysis revealed that the anchoring structures predominately included cross-hatched grooves and their population amounted to about 1,000 per cm. The coupons were encapsulated to a coating thickness of  ̃50 micron by depositing fine-grained Ni-20Fe alloys (average grain size  ̃20 nm, CLTE:  ̃11×10−6 K−1) from a modified Watts nickel bath and using a Dynatronix (Dynanet PDPR 20-30-100) pulse power supply as described in U.S. Patent Publication No. U.S. 2006-0135281-A1, published Jun. 22, 2006, the whole of which is incorporated herein by reference.
The metal clad articles had a yield strength of 606 MPa, an ultimate tensile in strength of 614 MPa, a Young's modulus of 71 GPa and an elastic limit of 0.9%.
Coated samples were exposed to a thermal cycling test which involves vertical submersion into liquid nitrogen (T=−196° C.) for one minute, immediately followed by submersion in hot water (T=90° C.) for one minute. After ten cycles the sample is inspected for delamination, blistering, cracks and the like and the relative displacement of the coating determined. Thirty such thermal cycles were performed. All samples passed the liquid nitrogen/hot water cycling test without delamination. In addition, another set of samples was exposed to 10 thermal cycles according to the ANSI/ASTM specification B604-75 section 5.4 Thermal Cycling Test for Service Condition 4 (85° C. to −40° C.) without failure. Thereafter, the adhesion between the metallic layer and the polymeric substrate was determined using ASTM D4541-02 Method E using the self alignment adhesion tester type V described in Annex A5, specifically the “PosiTest AT Adhesion Tester” available from the DeFelsko Corporation of Ogdensburg, N.Y., USA. The data are displayed in Table 3.







TABLE 3







Thermal Cycling/Adhesion Test Results

















Thermal Cycling Test
ANSI/ASTM specification
Pull-Off Strength



Min/Max
Coating

(−196/90° C.)
B604-75 section 5.4
ASTM D4541-02



Substrate
Chemistry
Coating
Performance after 10
Thermal Cycling Test/
Method E after 10


Substrate
CLTE
(Average Grain
CLTE
cycles/Displacement
SC4; 10 cycles/
cycles of ASTM


Chemistry
[10−6 K−1]
Size in nm)
[10−6 K−1]
  L/L [%]
Displacement   L/L [%]
B604-75/SC4 [psi]





Graphite Fiber/
5/60
80Ni—20Fe
11
Pass/~0
Pass/~0
350


Epoxy Composite

(15 nm)









WORKING EXAMPLE III
Fine-grained Ni-58Fe Coated Carbon Fiber Cloth Reinforced Bismaleimide Polymer Composite Activated by Various Chemical and Anodically Assisted Chemical Etching Methods, Use of a Metalizing Layer
3.75×8.75 cm coupons were cut from an 6 mm thick fully cured conductive carbon-fiber reinforced plastic (CFRP) sheet of HTM 512, a bismaleimide pre-impregnated carbon fiber cloth composite used in high temperature resistant composite tooling available from the Advanced Composites Group Ltd. of Heanor, Derbyshire, United Kingdom. The CLTE of the substrate material is 3×10−6 K−1 in the plane and 70×10−6 K−1 in the direction normal to the plane. The initial substrate preparation procedure was as follows: (i) mechanically abrading all exposed surfaces using 320 grit to a uniform finish, (ii) scrubbing with steel wool and Alconox cleaner, followed by a rinse in deionized water and (iii) rinsing with isopropanol, followed by drying. Thereafter the composite coupons were processed in various etching solutions, namely an alkaline permanganate etch, a chromic acid etch, a sulfuric acid etch and a sodium hydroxide etch with and without anodic assist. Microscope analysis revealed anchoring structures which included cross-hatched grooves, cavities, pitted anchoring structures and protruding anchoring fibers and, depending on the sample, their population amounted to between about 3,000 and about 25,000 per cm for the samples which passed the thermal cycling test. Subsequently, the samples were metalized using a commercial silvering solution (available from Peacock Laboratories Inc., of Philadelphia, Pa., USA; average grain size 28 nm) and coated on one side with a 50 μm thick layer of fine-grained Ni-58Fe (CLTE:  ̃2×10−6 K−1, average grain size  ̃20 nm) according to US Patent Publication No. US 2005-0205425 A1, published Sep. 22, 2005.
The metal clad articles had a yield strength of 604 MPa, an ultimate tensile strength of 608 MPa, a Young's modulus of 71 GPa and an elastic limit of 0.9%.
Following plating, the adhesion strength was measured using ASTM D4541-02 Method E “Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers” using the “PosiTest AT Adhesion Tester” made by DeFelsko Corporation of Ogdensburg, N.Y., USA. In all cases debonding occurred between the polymer material surface and the adjacent metal layer. Samples were also exposed to 10 cycles according to ANSI/ASTM specification B604-75 section 5.4, service condition 4.
For each different etch solution chemistry, CFRP samples were tested under 3 different conditions: 1) passive dip in solution for 5 min, 2) anodically polarized at 50 mA/cm2 for 5 min, and 3) anodically polarized at 100 mA/cm2 for 5 min. Following etching the samples were neutralized, as appropriate and then rinsed in deionized water and the resulting mass loss from etching was documented.
The etch compositions, etching conditions, mass loss during etching and adhesion strength after etching are shown in the Tables 4-7 below. In this experiment only the permanganate etch under all conditions tested and the sulfuric acid control etch were found to result in a weight loss. The slight increase in mass in the other samples may be a result of “swelling” (absorption of liquid) during etching which is known to occur with various polymer substrates including fiber reinforced epoxy composites.
In all etch solutions investigated a significant increase in adhesion strength is obtained (>30%) by applying an anodic current assist during etching without any increase in etching time. The adhesion strength was found to increase with increased anodic assisted etch current density (100 mA/cm2 compared to 50 mA/cm2). The oxidizing etch solutions (permanganate and chromic) were found to provide the highest adhesion values.
All samples were also exposed to 10 cycles according to ANSI/ASTM specification B604-75 section 5.4, service condition 4 and all samples, except for the sulfuric acid etch and NaOH etch for dipping only, passed the test.







TABLE 4





Permanganate Etch


















Solution Type
Chemical Composition







MacDermid
M-Permanganate: 60 g/L



Permanganate Etch
M-79224: 60 g/L



5 min @ 45° C.
D.I. Water: 940 g/L















Thermal Cycling Test




(ANSI/ASTM B604-75



Adhesion
section 5.4); Service



(ASTM D4541-
Condition 4, 10 Cycles/


Etching Type
02 Method E) [psi]
Displacement   L/L [%]





Dip only
433
Pass/~0


Dip & Anodic Etch @
668
Pass/~0


50 mA/cm2


Dip & Anodic Etch @
1069 
Pass/~0


100 mA/cm2
















TABLE 5





Sulfuric Acid Etch


















Solution Type
Chemical Composition







Sulfuric Acid Etch
H2SO4: 5% (in D.I. water)



5 min @ 25° C.















Thermal Cycling Test




(ANSI/ASTM B604-75



Adhesion
section 5.4); Service



(ASTM D4541-
Condition 4, 10 Cycles/


Etching Type
02 Method E) [psi]
Displacement   L/L [%]





Dip only
169
Failure/delamination


Dip & Anodic Etch @
227
Pass/~0


50 mA/cm2


Dip & Anodic Etch @
328
Pass/~0


100 mA/cm2
















TABLE 6





Sodium Hydroxide Etch


















Solution Type
Chemical Composition







Sodium Hydroxide
NaOH: 25% (in D.I. water)



Etch 5 min @ 25° C.















Thermal Cycling Test




(ANSI/ASTM B604-75



Adhesion
section 5.4); Service



(ASTM D4541-
Condition 4, 10 Cycles/


Etching Type
02 Method E) [psi]
Displacement   L/L [%]





Dip only
185
Failure/delamination


Dip & Anodic Etch @
409
Pass/~0


50 mA/cm2


Dip & Anodic Etch @
643
Pass/~0


100 mA/cm2
















TABLE 7





Chromic Acid Etch


















Solution Type
Chemical Composition







Chromic Acid Etch 5 min
Chromic acid: 5%



@ 50° C.




Phosphoric acid: 15%




Sulfuric acid: 55% (in D.I. water)















Thermal Cycling Test




(ANSI/ASTM B604-75



Adhesion
section 5.4); Service



(ASTM D4541-
Condition 4, 10 Cycles/


Etching Type
02 Method E) [psi]
Displacement   L/L [%]





Dip only
408
Pass/~0


Dip & Anodic Etch @
772
Pass/~0


50 mA/cm2


Dip & Anodic Etch @
893
Pass/~0


100 mA/cm2









WORKING EXAMPLE IV
Graphite or Glass-filled Polymeric Composites Activated by Acid Etching and Coated with an Amorphous Ni-based Metallic Layer or Coated with an Intermediate Conductive Layer and a Fine-grained Ni Layer
5 cm by 5 cm coupons (thickness 2 mm) of various substrates were suitable pretreated using a chromic acid etch solution as per Working Example III Table 7 and coated with various fine-grained materials available from Integran Technologies Inc. (www.integran.com; Toronto, Canada) to a metallic layer thickness of  ̃100 micron. Substrate materials included graphite/epoxy sourced from Newport Adhesives and Composites, Irvine, Calif., USA and glass fiber/polyamide composite coupons sourced from BASF, Florham Park, N.J., USA. After appropriate chemical activation (chromic acid etch according to Table 7, dip only) all samples subjected to electroplating were metalized using a commercial silvering solution (available from Peacock Laboratories Inc., of Philadelphia, Pa., USA; average grain size 28 nm). Microscope analysis revealed anchoring structures that included cross-hatched grooves, cavities, pitted anchoring structures and protruding anchoring fibers and, depending on the sample, their population amounted to between about 3,000 and about 10,000 per cm. Subsequently, fine-grained Ni-based metallic layers were deposited from a modified Watts bath as described in U.S. Patent Publication No. US 2005-0205425 A1, published Sep. 22, 2005. Amorphous Ni-based layers (−20 micron thick Ni-7P) were deposited directly onto the etched polymeric substrates using an electroless nickel bath available from MacDermid Inc., Waterbury, Conn., USA.
Table 8 summarizes the mechanical properties of the metal clad polymer articles.







TABLE 8







Mechanical Properties of the metal clad polymer articles.














Yield
Ultimate
Young's



Substrate (2 mm
Coating Chemistry
Strength
Tensile
Modulus
Elastic


thick)
(20 micron thick)
[MPa]
Strength [MPa]
[GPa]
Limit [%]















Glass
Ni—7P (amorphous)
146
146
6.6
2.2


Fiber/Polyamide
Without Ag


Composite
metalizing layer


Glass
Ni (15 nm)
148
152
7.4
2.0


Fiber/Polyamide
With Ag metalizing


Composite
layer


Glass
50Ni—50Fe (20 nm)
150
154
7.0
2.1


Fiber/Polyamide
With Ag metalizing


Composite
layer


Graphite
Ni—7P (amorphous)
601
601
70
0.9


Fiber/Epoxy
Without Ag


Composite
metalizing layer


Graphite
Ni (15 nm)
603
608
71
0.9


Fiber/Epoxy
With Ag metalizing


Composite
layer


Graphite
50Ni—50Fe (20 nm)
605
610
70
0.9


Fiber/Epoxy
With Ag metalizing


Composite
layer









The coated samples were exposed to the thermal cycling test described above. The adhesion strength was measured using ASTM D4541-02 Method E using the “PosiTest AT Adhesion Tester” available from the DeFelsko Corporation of Ogdensburg, N.Y., USA. In all cases debonding occurred between the polymer material surface and the immediately adjacent metal layer. The data displayed in Table 9 indicate that acceptable thermal cycling performance is achieved. All samples were also exposed to 10 cycles according to ANSI/ASTM specification B604-75 section 5.4, service condition 4 without failure.







TABLE 9







Thermal Cycling/Adhesion Test Results
















Thermal







Cycling Test
Pull-Off






(−196 to 90° C.)
Strength



Min/Max


Performance
ASTM



Substrate
Coating Chemistry
Coating
after 10 cycles/
D4541-02


Substrate
CLTE
(Average grain size
CLTE
Displacement
Method E


Chemistry
[10−6K−1]
in nm)
[10−6K−1]
  L/L [%]
[psi]





Glass
20/110
Ni—7P (amorphous)
20
Pass/~0
300


Fiber/Polyamide

Without Ag


Composite

metalizing layer


Glass
20/110
Ni (15 nm)
13
Pass/~0
300


Fiber/Polyamide

With Ag metalizing


Composite

layer


Glass
20/110
50Ni—50Fe (20 nm)
10
Pass/~0
300


Fiber/Polyamide

With Ag metalizing


Composite

layer


Graphite
5/55
Ni—7P (amorphous)
20
Pass/~0
620


Fiber/Epoxy

Without Ag


Composite

metalizing layer


Graphite
5/55
Ni (15 nm)
13
Pass/~0
620


Fiber/Epoxy

With Ag metalizing


Composite

layer


Graphite
5/55
50Ni—50Fe (20 nm)
10
Pass/~0
620


Fiber/Epoxy

With Ag metalizing


Composite

layer









WORKING EXAMPLE V
Coating of Fully-cured and Partially-cured Graphite Reinforced Polymer Composites with a Silver (Ag) Intermediate Layer and a Fine-Grained Ni—Fe Layer, Including Heat-treatment of the Partially-cured Coated Part
Three 15×15 cm samples of 6 mm thick conductive carbon-fiber reinforced plastic (CFRP) sheet (CLTE: in the plane 3×10−6 K−1 and CLTE:  ̃60×10−6 K−1 normal to the plane) were obtained from Janicki Industries of Sedro-Wooley, Wash., USA. Two of the panels were only “partially” cured, while the third panel was “fully” cured. The coupons were ground on one side with 80 grit SiC paper to a consistent surface roughness, cleaned with Alconox and steel wool, followed by ultrasonically cleaning in deionized water for 5 minutes. The samples was then rinsed in isopropanol, dried and degreased with 1,2-dichloroethane to remove any residual oils and/or films.
The CFRP panels were then chemically etched in a standard acid sulfo-chromic etch solution consisting of 300 g/L chromic acid and 250 g/l sulfuric acid in deionized water. After surface preparation the surface roughness of the coupons was determined to be Ra  ̃2.0 micron and Rymax ̃10.0 micron. Microscope analysis revealed that the anchoring structures included cavities and pitted anchoring structures and their population ranged from about 1,000 to about 25,000 per cm. Following etching, the samples were rinsed in deionized water and submerged in neutralizer solution consisting of 5 g/l of sodium metabisulfite for 5 minutes at room temperature. After neutralizing, the samples were rinsed with deionized water and metalized using a commercial silvering solution (available from Peacock Laboratories Inc., of Philadelphia, Pa., USA; average grain size 28 μm) and coated with 50 μm of fine-grained Ni (average grain size  ̃15 nm, CLTE:  ̃13×10−6 K−1) according to the process of US Patent Publication No. US 2005-0205425 A1, published Sep. 22, 2005.
The metal clad articles had a yield strength of 602 MPa, an ultimate tensile strength of 606 MPa, a Young's modulus of 7.4 GPa and an elastic limit of 0.9%.
One of the panels was then subjected to a post-coating heat-treatment in a drying oven for an additional 2 hours at 177° C. to fully cure the partially cured panel. The pull-off adhesion strength of the coatings of the three CFRP samples was then measured following ASTM D4541-02 “Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers” using the “PosiTest AT Adhesion Tester” available from the DeFelsko Corporation of Ogdensburg, N.Y., USA.
The pull-off adhesion strength for the three samples is summarized in the Table 10. The pull-off strength for the “partially” cured sample was found to be significantly higher than that of the “fully” cured sample. The data also shows that a further increase in adhesion strength can be obtained by fully curing the “partially” cured CFRP panel after the metal coating. All samples were also exposed to 10 cycles according to ANSI/ASTM specification B604-75 section 5.4, service condition 4 without failure.







TABLE 10







Pull-Off Strength Data (ASTM D4541-02) for Samples.











Thermal Cycling Test




(ANSI/ASTM B604-75




section 5.4); Service



Pull-off Strength
Condition 4, 10



(ASTM D4541-02)
Cycles/Displacement



[psi]
  L/L [%]













Coated of fully cured
490
Pass/~0


CFRP-substrate


Coated of partially cured
1542
Pass/~0


CFRP-substrate


Coated of partially cured
2078
Pass/~0


CFRP-substrate with


post-plate heat treatment


(2 hours at 177° C.)









WORKING EXAMPLE VI
Glass-filled Polymer Composites Activated by Acid Etching and Coated with an Amorphous Ni-Based Intermediate Conductive Layer and a Fine-grained Ni Layer, Followed by Post Plate Heat-treatment


    
    
        5 cm by 5 cm coupons (thickness 2 mm) were cut from a commercially available 14% glass-filled polyamide substrate (Caspron®, BASF, Florham Park, N.J., USA.). The CLTE of the coupon in the plane was 32×10−6K−1 and normal to the plane 70×10−6 K−1. Samples were suitable pretreated using a chromic acid etch solution as per Working Example III Table 7 (dip only). After neutralizing, the samples were rinsed with deionized water and metalized using a commercial amorphous electroless Ni-7P coating available from MacDermid Inc. of Waterbury, Conn., USA and thereafter coated with 20 μm thick fine-grained nickel (average grain size  ̃20 nm, CTLE 13×10−6 K−1) according to the process of US Patent Publication No. US 2005-0205425 A1, published Sep. 22, 2005, available from Integran Technologies Inc. (www.integran.com; Toronto, Canada).
    
    


The metal clad articles had a yield strength of 148 MPa, an ultimate tensile strength of 152 MPa, a Young's modulus of 7.4 GPa and an elastic limit of 2.0%.
Microscope analysis revealed that anchoring structures included cross-hatched grooves, cavities, pitted anchoring structures and protruding anchoring fibers and amounted to between about 10,000 and 15,000 per cm. Selected samples were heat treated at 80° C. and the adhesion and thermal cycling performance determined. The peel and pull-off adhesion strength of the samples was then measured following ASTM D4541-02 “Standard Test Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers” and ASTM B533-85 (2004) “Standard Test Method for Peel Strength of Metal Electroplated Plastics” using an Instron 3365 testing machine equipped with the 90 degree peel test fixture, and a 5KN load cell, available from Instron Corporation, Norwood, Mass., USA. In all cases debonding occurred between the polymer material surface and the immediately adjacent metal layer. The data displayed in Table 11 indicate that acceptable thermal cycling performance is achieved. All samples were also exposed to 10 cycles according to ANSI/ASTM specification B604-75 section 5.4, service condition 4 without failure. It is noted that post-plating heat-treatment modestly enhances the pull-off strength whereas the peel strength drastically deteriorates. As highlighted above and illustrated in Example 1 there is no correlation between pull-off and peel strength data.







TABLE 11







Thermal Cycling/Adhesion Test Results



















Thermal Cycling Test


Min/Max
Coating

Post Plating


(ANSI/ASTM B604-75


Substrate
Chemistry
Coating
Heat-Treatment
Pull-Off Strength
Peel Strength
section 5.4); Service


CLTE
(Average grain
CLTE
Duration at
ASTM D4541-02
(ASTM B533-85)
Condition 4, 10 Cycles/


[10−6 K−1]
size in nm)
[10−6 K−1]
80° C. [hrs]
Method E [psi]
[N/cm]
Displacement   L/L [%]
















32/70
Ni (15 nm)
13
0
862
9
Pass/~0



With NiP



metalizing



layer


32/70
Ni (15 nm)
13
1
932
7
Pass/~0



With NiP



metalizing



layer


32/70
Ni (15 nm)
13
2
885
5
Pass/~0



With NiP



metalizing



layer









WORKING EXAMPLE VII
Fine-grained Co—P Metal Layer with a Rough Surface Produced Electrochemically Prior to Applying a Polymer Based Backing Layer
A metal-clad polymer part was fabricated from two components, namely a face plate comprised of a durable electroformed fine-grained Co-2P alloy (15 nm average grain size, CLTE in plane and normal to it:  ̃15×10−6 K−1), and a polymer backing structure comprising a thermoplastic polymer (polypropylene, CLTE in plane and normal to it:  ̃85×10−6 K−1). Rather than coating the activated polymer substrate with a fine-grained metal, the layers were applied in reverse order, namely the first step entailed plating the fine-grained Co-2P alloy layer (average grain size 15 nm) according to US Patent Publication No. US 2005-0205425 A1, published Sep. 22, 2005, onto a polished temporary titanium substrate. After building up the fine-grained metallic layer to a thickness of approximately 250 microns, the applied current density was raised substantially to deposit a rough “bonding surface” with anchoring structures including protrusions and dendritic nodules with a porous substructure and, depending on the sample, their population count ranged between about 100 and about 3,000 per cm. After plating, the surface roughness of the metallic layer, to serve as interface with the polymeric layer, was determined to be Ra  ̃125 micron and Rymax ̃250 micron. As outlined, the important feature of the design is to purposely create a rough surface on the backside of the faceplate which allows for excellent adhesion between the metal faceplate and the polymer backing structure. A polypropylene substrate backing was applied to the rough side of the fine-grained metal layer in a subsequent step by compression molding to an ultimate thickness of 6 mm. Metal-clad polymer samples exposed to 10 cycles according ANSI/ASTM specification B604-75 section 5.4, service condition 4, did not fail and the adhesion strength values that have been obtained using ASTM D4541-02 Method E all exceeded 300 psi. The metal clad articles had a yield strength of 96 MPa, an ultimate tensile strength of 113 MPa, a Young's modulus of 6.5 GPa and an elastic limit of 1.0%.
Variations
The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be so limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of the invention.

## Claims

1. A metal-clad polymer article comprising:
(i) a polymeric material which at room temperature in at least one direction has a coefficient of linear thermal expansion at room temperature in the range between 30×10−6 K−1; and 500×10−6 K−1; and
(ii) a metallic material having a microstructure which is fine-grained with an average grain size between 2 and 5,000 nm and/or an amorphous microstructure, said metallic material forming a metallic layer and said metallic material having a coefficient of linear thermal expansion at room temperature in all directions of −5.0×10−6 K−1and 25×10−6 K−1, wherein said metallic material consists essentially of a metal selected from the group consisting of Ag, Al, Au, Co, Cr, Cu, Fe, Ni, Mo, Pb, Pd, Pt, Rh, Ru, Sn, Ti, W, Zn and Zr or comprises an alloy containing at least one metal selected from the group consisting of Ag, Al, Au, Co, Cr, Cu, Fe, Ni, Mo, Pb, Pd, Pt, Rh, Ru, Sn, Ti, W, Zn and Zr;
(iii) with or without at least one intermediate layer between the polymeric material and the metallic material layer;
(iv) an interface formed between the polymeric material and the metallic material or an interface between the polymeric material and said at least one intermediate layer if present and in interface between said at least one intermediate layer if present and the metallic material, at least one of said interfaces containing an anchoring structure comprising recesses and/or protrusions to increase the interface surface area; and
(v) wherein said metal-clad polymer article exhibits a pull-off strength between the polymeric material and the metallic material or a pull-off strength between said at least one intermediate layer if present and the metallic material or a pull-off strength between said at least one intermediate layer if present and the polymeric material exceeding 200 psi as determined by ASTM D4541-02 Method A-E.

2. The article according to claim 1, wherein said metallic material layer comprises a metal alloy, and said metal alloy in said metallic material layer comprises at least one element selected from the group consisting of B, C, H, O, P and S.

3. The article according to claim 2, wherein said metallic material layer further comprises particulate addition and said particulate addition comprises at least one material selected from the group consisting of a metal; a metal oxide, a carbide; a carbon material; ceramic material; glass; and a polymer material.

4. The article according to claim 1, wherein said polymeric material comprises a polymeric material selected from the group consisting of epoxy resins, phenolic resins, urea resins, melamine resins, thermoplastic polymers, polyolefins, polyethylenes, polypropylenes, polyamides, poly-ether-ether-ketones, mineral filled polyamide resin composites, polyphthalamide, polyphthalates, polystyrene, polysulfone, polyimides, neoprenes, polyisoprenes, polybutadienes, polyisoprenes, polyurethanes, butadiene-styrene copolymers, chlorinated polymers, polyvinyl chloride, fluorinated polymers, polytetrafluoroethylene, polycarbonates, polyesters, liquid crystal polymers, partially crystalline aromatic polyesters based on p-hydroxybenzoic acid, and acrylonitrile-butadiene-styrene.

5. The article according to claim 1, said article comprising said at least one intermediate layer.

6. The article according to claim 5, wherein said at least one intermediate layer is a metallic layer comprising at least one element selected from the group consisting of Ag, Ni, Co and Cu.

7. The article according to claim 5, wherein said at least one intermediate layer comprises an adhesive layer.

8. The article according to of claim 1, wherein said article is an automotive, aerospace, or sporting component.

9. The article according to claim 1, wherein said article is selected from the group consisting of cylindrical objects; medical equipment; sporting goods; components and housings for electronic equipment; automotive components; molds and molding tools; aerospace components, and military products.

10. The article according to claim 9, wherein said polymeric material layer comprises glass fibers and/or a carbon-containing material selected from the group consisting of graphite, graphite fibers, carbon, carbon fibers and carbon nanotubes.

11. The article according to claim 1, wherein said article has a tubular structure and said metallic material layer extends over at least part of the inner or outer surface of said tubular structure.

12. The article according to claim 1, wherein the metallic material layer has a thickness between 10 and 500 microns.

13. The article according to claim 1, wherein the anchoring structure comprises at least one shape selected from the group consisting of ink bottle shaped cavities, pitted anchoring structures, anchoring surfaces with protruding anchoring fibers; grooved, roughened and/or etched anchoring surface structures; and dimples and mounds.

14. The article according to claim 13, wherein the anchoring structure has a population of recesses and/or protrusions in the range of 1 to 10,000,000 per mm2 of interface(s) area, said recesses and/or protrusion having a height/depth range between 10 nm and 1 mm and a diameter ranging between 50 nm and 1 mm.

15. The article according to claim 1 wherein a displacement of said metallic material layer relative to the polymeric material or relative to said at least one intermediate layer after at least one temperature cycle according to ASTM B553-71 service condition 1, 2 3 or 4 is less than 2%.

16. The article according to claim , wherein said article exhibits no delamination after said article has been exposed to at least one temperature cycle according to ASTM B553-71 service condition 1, 2, 3 or 4.

17. The article according to claim 1, wherein said metallic material comprises multi-layer laminates.

18. The article according to claim 17, wherein said metallic material comprises fine-grained and amorphous layers.

19. The article according to claim 1, wherein said metallic material comprises graded layers.